Dimensionally stable shaped hollow sections from aliphatic polyamides and their applications

ABSTRACT

Polyamide plastic fuel lines which are dimensionally stable and resistant to fuels, alcoholic fuels and alcohols as fuels are prepared from aliphatic high molecular weight polyamides. The fuel lines are prepared by extruding a hot melt of the polyamide, sizing through a die having a diameter in excess of the given diameter of the fuel line, cooling the fuel line in a cooling bath, removing the fuel line from the bath and sizing the fuel line adiabatically through a disk having a diameter less than the given diameter.

CROSS-REFERENCE TO RELATED APPLICATIONS

This is a division of application Ser. No. 464,772, filed Feb. 7, 1983,now U.S. Pat. No. 4,519,968.

Applicants claim priority under 35 USC 119 for applications No. P 32 06131.5, filed Feb. 20, 1982, and No. P 32 43 612.2, filed Nov. 25, 1982,in West Germany.

BACKGROUND OF THE INVENTION

The field of the invention is shaped, hollow sections, in particulartubes, which are made from polyamides and used as supply lines for thefuels of internal combustion engines.

These polyamides have as the fundamental unit (repeating unit) lactamsor omega-amino-carboxylic-acids having at least five carbon atoms percarbon amide group, such as nylon-6, nylon-8, nylon-11, or nylon-12, orpolyamides from equivalent quantities of aliphatic dicarboxylic acidsand aliphatic diamines which together have at least 12 carbon atoms, forinstance nylon-6-6, nylon-6-8, nylon-6-9, nylon-6-10, and nylon-6-12.

It has been found that fuel lines made from these polyamides undergo alongitudinal expansion due to the action from fuels, used for internalcombustion engines, in particular with the use of fuels containingalcohols and consisting of alcohols. This longitudinal expansion can beof the order of a few percent. Due to this longitudinal expansion, thelines sag in between the supports, and, accordingly, must be viewed as asource of danger due to rupture and fires resulting therefrom.

The state of the art of extruding tubing and pipe from polyamideplastics may be ascertained by reference to the Kirk-Othmer"Encyclopedia of Chemical Technology," 2nd Edition, Volume 16, (1968),under the section "Polyamide (Plastics)," pages 88-105, particularlypages 89 and 92--nylon-6, nylon-6-6, polylauryl-lactam (nylon-12),polyundecanamide (nylon-11), and additives, and page 99 --pipe andtubing extrusion, the disclosures of which are incorporated herein.

SUMMARY OF THE INVENTION

Having in mind the limitations of the prior art it is an object toproduce shaped hollow objects from polyamide plastics which aredimensionally stable to fuels and alcoholic fuels.

It is a particular object of the present invention to provide fuel linesfrom polyamide plastics which are dimensionally stable with respect tofuels containing alcohols or to alcohols themselves, whereby they incurno disadvantageous elongation.

These objects are achieved by first extruding the polyamide into shapedhollow sections evincing a diameter in excess of a given value, and bysubsequently sizing the cooled hollow shaped sections to the givendimension.

The term aliphatic polyamides as used in the present invention having atleast 5 carbon atoms per carbon amide group means nylon-6(polycaprolactam), nylon-8 (polysuberolactam), nylon-11(polyundecanamide) and especially nylon-12 (polylauryllactam),furthermore polyamides from equivalent quantities of aliphaticdicarboxylic acids and aliphatic diamines which together have at least12 carbon atoms, for instance nylon-6-6 (of hexamethylenediamine andadipic-acid), nylon-6-8 (of hexamethylenediamine and suberic acid),nylon-6-9 (of hexamethylenediamine and azelaic acid), nylon-6-10 (ofhexamethylenediamine and sebacic acid), and nylon-6-12 (of hexamethylenediamine and decanoic-dicarboxylic-acid).

BRIEF DESCRIPTION OF THE DRAWINGS

The new and unexpected results of the present invention are shown in aseries of plots of % elongation versus exposure times in days, wherein:

FIG. 1 is a comparison between plot 1.1 of a stabilized nylon 12according to the present invention, and plot 1.2 of the state of the artboth used with M 15 VK carburetor fuel containing 15% methanol;

FIG. 2 is a comparison between plot 2.1 of a stabilized nylon 11according to the present invention and plot 2.2 of the state of the artboth used with M 15 VK carburetor fuel containing 15% methanol;

FIG. 3 is a comparison between plot 3.1 of a stabilized nylon 12containing 8% plasticizer according to the present invention and plot3.2 of the state of the art both used with M 15 VK carburetor fuelcontaining 15% methanol;

FIG. 4 is a comparison as in FIG. 1 except that M 100 VK carburetor fuelcontaining 100% methanol is used;

FIG. 5 is a comparison as in FIG. 2 except that M 100 VK carburetor fuelcontaining 100% methanol is used;

FIG. 6 is a comparison as in FIG. 3 except that M 100 VK carburetor fuelcontaining 100% methanol is used;

FIG. 7 is a comparison as in FIG. 1 except that Super VK commercial fuelaccording to German Industrial Standard DIN 51,600 is used;

FIG. 8 is a comparison as in FIG. 2 except that Super VK commercial fuelaccording to German Industrial Standard DIN 51,600 is used; and

FIG. 9 is a comparison as in FIG. 3 except that Super VK commercial fuelaccording to German Industrial Standard DIN 51,600 is used.

FIGS. 10, 11 and 12 are comparisons between the plots 4.1 fornylon-6-12, 5.1 for nylon-6-8 and 6.1 for nylon-6 according to thepresent invention and the plots 4.2 for nylon-6-12, 5.2 for nylon-6-8and 6.2 for nylon-6 of the state of art used with M 15 VK carburetorfuel containing 15% methanol.

FIGS. 13 and 14 are comparisons between the plots 7.1 for stabilizednylon-12--for another excess diameter prior to the secondcalibration--and 8.1 for nylon-12 containing 15% plasticizer accordingto the present invention and 7.2 for stabilized nylon-12 and 8.1 fornylon 12 containing 15% plasticizer of the state of art in Normalcarburetor fuel according to DIN (German Industrial Standard) 51 600.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

To the extent required the polyamide plastics of the present inventioncontain conventional accessories such as stabilizers, antiageing means,or mixtures thereof. They may also contain other additives such aspigments. Also the present invention contemplates the use of suitableplasticizers such as the derivatives of aromatic sulfonic acid amides orof 4-hydroxybenzoic acid, in particular N-butylbenzenesulfonic acidamide or 4-hydroxybenzoic acid octylester. These derivatives are presentin amounts up to 20 percent by weight, especially from 2 to 10% byweight of the total mass of the molding composition. In other words,such a plasticized polyamide substance consists of a polyamide having upto 80% by weight and of a plasticizer up to 20% by weight and inaddition to the conventional accessories. Copolyamides having slightamounts of comonomers are not excluded provided they are suitable forthe intended application.

The shaped hollow section (tube) is manufactured in conventional mannerusing an extruder with a tube head, a sizing device, a tank for coolingwater and removal means. The polyamide melt issues from the tube die ofthe tube head at a temperature between 180° and 280° C. is shaped in thesizing device, set for an excess dimension compared to the givendiameter being set. Thereupon the shaped hollow section (tube) is cooledin the water tank.

It is known to the state of the art to first extrude hollow nylonsections, heated to be plastically deformable, at about 1.3 times thedesired diameter and to insert this tubing heated to be plasticallydeformable into a gauging device located in a water bath. In thisgauging device, the tubing which is heated to be plastically deformableis reduced to the desired lesser diameter and is simultaneously cooled.

The gauging device has a diameter somewhat larger than the desiredtubing diameter (Kirk-Othmer, i.b.i.d., page 99). Such hollow nylonsections lack dimensional stability with respect to fuels and theyundergo an undesired longitudinal expansion when in contact with suchfuels.

According to the present invention, the cooled tubing, having an excesssize with respect to the rated diameter, is introduced by means of atake-off device into a second gauging system where it is adjusted to therated diameter. This takes place without external heat supply(adiabatically).

Advantageously the second gauging is by means of disk gauging, whichcontrary to the cited state of the art has a somewhat lesser diameterthan the rated tubing diameter.

The required excess dimension of the shaped hollow section (tube) priorto the second sizing procedure depends on the processing conditions, onthe composition of the polyamide molding substance and to some extent onthe medium for which the line is intended, and is adjusted accordingly.The excess size with respect to the given diameter can amount to 5 to20%, in particular from 10 to 15%.

The temperature of the cooling water and the length of the cooling bathare not critical, however, the temperature should be kept approximatelyconstant. When the cooled shaped hollow section (tube) is made to passthrough the second sizing device, the tube will rise slightly intemperature. Thereby, a somewhat elastic reset of the diameter takesplace after the gauging procedure. Thereafter the tube can be passedonce more through a bath of cooling water for further cooling.

Accordingly, the inside diameter of the second gauging device must beless than the desired rated diameter of the shaped hollow section(tube). As a rule this inside diameter is 2 to 15%, preferably 5 to 10%,less than the rated diameter.

The following specific examples further illustrate the presentinvention:

EXAMPLES

A tube of the invention (Example 1.1) and a tube of the state of the art(control test 1.2) both made of stabilized nylon-12 are produced using asingle-screw extruder with tube head.

The barrel inside diameter of the extruder is 45 mm in both cases;furthermore the ratio of barrel length to inside diameter is 25, and theextruder is provided with triple zone screw having a depth-of-threadratio of 3:1. The die of the tube head has an outside diameter of 16 mmand an inside diameter of 12 mm. All extruder heaters are set at 240° C.The speed of the feeding screw is 50 rpm.

In Example 1.1 (invention), the melt issuing from the die of the tubehead is made to pass into the gauging tube of a vacuum gauging systemwith an inside diameter of 9.5 mm. The reduced pressure in the vacuumgauging system is 0.36 bars. A tube with an outside diameter of 9.0 mmand a wall thickness of 1 mm is obtained. This tube is cooled in a watercooling bath which is 4 m long. Then this cooled tube is moved through asecond gauging device with an inside diameter of 7.5 mm. With adiabaticheating, the rated tube diameter of 8 mm having a 1 mm wall thickness isthen obtained. Next, the tube is taken off by means of a take-off systemand cut to the proper length.

In the control test 1.2, the melt issuing from the die of the tube headis made to pass into the gauging tube of a vacuum gauging system with aninside diameter of 8.5 mm. The tube is obtained at a reduced pressure of0.25 bars in the absence of a second gauging procedure with the rated 8mm outside diameter and 1 mm wall thickness. This tube is cooled in a 4m long cooling-water bath, taken off with the take-off system and thencut to the proper length.

Examples 2.1 through 8.1 (the invention) and control tests 2.2 through8.2 are carried out in similar manner. The substances used are astabilized nylon-11 (2.1 and 2.2), a stabilized nylon-12 containing aplasticizer (3.1 and 3.2), a nylon 6-12 (4.1 and 4.2), nylon 6-8 (5.1and 5.2), nylon 6 (6.1 and 6.2), stabilized nylon-12 (for another excesssize prior to the second calibration) (7.1 and 7.2), and stabilizednylon-12 containing 14% of a plasticizer (8.1 and 8.2).

The test results are shown in the Table I below. D designates thediameter of the gauging tube of the first gauging device, d the diameterof the gauging disk of the second gauging procedure.

The tubes so made are cut to a length of 2,000 mm and filled withcarburetor fuels of the following designations:

M 15 VK, M 100 VK, Super VK and Normal VK where VK designates carburetorfuel and M 15 and M 100 designate, respectively, 15 and 100 methanolcontents, Super VK and Normal VK are commercial fuels according toGerman Industrial Standard DIN 51,600.

The fuels filled into the tubes are periodically replenished to achievetest conditions simulating practical conditions.

The changes in length of the tube segments were determined as a functionof the time of exposure. The results are plotted in FIGS. 1 through 14.

                  TABLE 1                                                         ______________________________________                                                          tube diameter (mm)                                          Example   D mm    d mm      per D per d                                       ______________________________________                                        1.1       9.5     7.5       9.0   8.0                                         1.2       8.5     --        8.0   --                                          2.1       9.3     7.5       9.0   8.0                                         2.2       8.5     --        8.0   --                                          3.1       8.8     7.6       8.5   8.0                                         3.2       8.5     --        8.0   --                                          4.1       9.5     7.5       9.0   8.0                                         4.2       8.5     --        8.0   --                                          5.1       9.0     7.5       8.5   8.0                                         5.2       8.5     --        8.0   --                                          6.1       9.5     7.5       9.0   8.0                                         6.2       8.5     --        8.0   --                                          7.1       9.3     7.5       8.8   8.0                                         7.2       8.5     --        8.0   --                                          8.1       7.0     5.6       6.7   6.0                                         8.2       6.4     --        6.0   --                                          ______________________________________                                    

What we claim is:
 1. The product obtained by the method formanufacturing shaped, hollow sections of polyamide plasticsdimensionally stable under influence of fuels for internal combustionengines and having a given diameter consisting of:(a) extruding a hotmelt of aliphatic polyamides having at least 5 carbon atoms per carbonamide group or polyamides from an aliphatic dicarboxylic acid and analiphatic diamine which together have at least 12 carbon atoms through atube die; (b) sizing said hot melt through a first gauging device havingan inside diameter greater than said given diameter; (c) cooling saidshaped, hollow sections obtained in a cooling bath; (d) removing thecooled, shaped hollow sections from the cooling bath; and (e) sizing thecooled, shaped hollow sections adiabatically through a second gaugingdevice having an inside diameter less than said given diameter wherebysaid given diameter is achieved.
 2. Fuel lines for conducting fuels tointernal combustion engines obtained by the method of manufacturingdimensionally stable fuel lines of polyamide plastics having a givendiameter consisting of:(a) extruding a hot melt of aliphatic polyamideshaving at least 5 carbon atoms per carbon amide group or polyamides froman aliphatic dicarboxylic acid and an aliphatic diamine which togetherhave at least 12 carbon atoms through a tube die; (b) sizing said hotmelt through a first gauging device having an inside diameter greaterthan said given diameter; (c) cooling said shaped, hollow sectionsobtained in a cooling bath; (d) removing the cooled, shaped hollowsections from the cooling bath; and (e) sizing the cooled, shaped hollowsections adiabatically through a second gauging device having an insidediameter less than said given diameter whereby said given diameter isachieved.
 3. Fuel lines for conducting fuels selected from the groupconsisting of alcoholic fuels and alcohols as fuels to internalcombustion engines obtained by the method of manufacturing dimensionallystable fuel lines of polyamide plastics having a given diameterconsisting of:(a) extruding a hot melt of aliphatic polyamides having atleast 5 carbon atoms per carbon amide group or polyamides from analiphatic dicarboxylic acid and an aliphatic diamine which together haveat least 12 carbon atoms through a tube die; (b) sizing said hot meltthrough a first gauging device having an inside diameter greater thansaid given diameter; (c) cooling said shaped, hollow sections obtainedin a cooling bath; (d) removing the cooled, shaped hollow sections fromthe cooling bath; and (e) sizing the cooled, shaped hollow sectionsadiabatically through a second gauging device having an inside diameterless than said given diameter whereby said given diameter is achieved.4. Fuel lines for conducting alcoholic fuels to internal combustionengines obtained by the method of manufacturing dimensionally stablefuel lines of polyamide plastics having a given diameter consistingof:(a) extruding a hot melt of aliphatic polyamides having at least 5carbon atoms per carbon amide group or polyamides from an aliphaticdicarboxylic acid and an aliphatic diamine which together have at least12 carbon atoms through a tube die; (b) sizing said hot melt through afirst gauging device having an inside diameter greater than said givendiameter; (c) cooling said shaped, hollow sections obtained in a coolingbath; (d) removing the cooled, shaped hollow sections from the coolingbath; and (e) sizing the cooled, shaped hollow sections adiabaticallythrough a second gauging device having an inside diameter less than saidgiven diameter whereby said given diameter is achieved.